Compositions, system and methods for introducing POE lubricant into an air-conditioning or a refrigeration system

ABSTRACT

Compositions, systems and methods for introducing lubricants, and additives, that are designed to work with environmentally friendly refrigerants into vehicle heat management systems including passenger compartment air conditioning (A/C) systems are disclosed. Methods for charging lubricants and specific additives using environmentally desirable (low GWP) refrigerant or refrigerant blend compositions into an environmentally friendly system, such as a system that uses HFO-1234yf, are also disclosed.

FIELD OF INVENTION

The present invention relates generally to compositions, systems andmethods of introducing lubricants, and additives, that are designed towork with environmentally friendly refrigerants into a conventional,hybrid, plug-in hybrid, or electric vehicle heat management systemsincluding passenger compartment air conditioning (A/C) or electricvehicle heat pump systems or stationary air-conditioning or stationaryrefrigeration systems. More specifically, this invention relates tomethods for charging lubricants and specific additives usingenvironmentally desirable (low GWP) refrigerant or refrigerant blendcompositions into an environmentally friendly system, such as a systemthat uses HFO-1234yf, HFO-1234ze, HFO-1234ze, HFO-1233zd, HFO-1336mzzZ,HFO-1336mzzE or blends containing these refrigerant or other low GWPrefrigerant blend components (ie those containing R-32, CO2, etc.). Thisinvention also relates to methods for charging refrigerants whichcontain lubricants and specific additives using environmentally into anenvironmentally friendly A/C system, such as an A/C system that usesHFO-1234yf

BACKGROUND INFORMATION

Since the mid-1990's, automotive air-conditioning (A/C) systems haveused refrigerant R-134a for vapor compression cycle. Now, due toenvironmental and societal pressures, global automotive manufacturersare transitioning to the low global warming potential (GWP) refrigerant,HFO-1234yf (2,3,3,3-tetrafluoropropene), as the vehicle A/C refrigerant.In the traditional vapor compression A/C system, the A/C compressorcirculates refrigerant through the A/C system to achieve cooling.Therefore, the A/C compressor is critical to A/C system operation. A/Ccompressors function as the heart of the A/C system pumping theoperating fluid through the system. Without correct operation of the A/Ccompressor, the A/C system would fail.

To operate accordingly, A/C compressors require lubricants with thecorrect physical parameters (viscosity, moisture, TAN, etc.). Thelubricant must completely circulate through the A/C system. Thelubricant must be to carried by the refrigerant from one part of thesystem to the next and the lubricant must also be able to carry therefrigerant from one part of the system to a different part of thesystem while providing lubrication when internal to the compressor.Therefore, mutual refrigerant/lubricant compatibility over the A/Csystem operating range of 0° C. to 40° C. is essential to effectiveoperation of the system.

As the automotive industry strives to meet ever increasing environmentalgoals, vehicle platforms are changing. Conventional vehicles usegasoline or diesel internal combustion engines (ICE) for vehiclepropulsion. However, due to environmental benefits, there is a definiteshift towards vehicle electrification. Automotive OEMs are designing newvehicles replacing all or part of the propulsion needs with electricmotors and batteries. Some vehicles still maintain an ICE and are notedas hybrid electric vehicle (HEV) or plug-in hybrids electric vehicle(PHEV) or mild hybrids electric vehicles (MHEV). Other vehicles arefully electric and have no ICE and these are denoted as full EVs.

All of the HEV, PHEV, MHEV and EVs use at least one electric motor,where the electric motor takes the place of the belt-driven pulleysfound on gasoline/diesel powered vehicles. It has been noted in variouspublications that polyalkylene glycol (PAG) lubricant cannot be used inHEV/PHEV/MHEV/EV systems. The insulation resistance of the electriccompressor can be reduced close to zero due to use of PAG. Morespecifically, the insulation resistance of an electric compressor can bereduced from over 10 Megohms to under 1 Megohms by use of 1% PAGlubricant. On the other hand, polyol ester or POE type lubricantsprovide high dielectric properties, which helps to maintain theintegrity of the compressor's electrical windings. Automotive originalequipment manufacturers (OEMs) typically add A/C lubricants during theinitial vehicle A/C filling process. A/C systems may require repair dueto a component failure (hose or line break) or vehicle accident whichcompromises the A/C system. Typically, the automotive aftermarket orservice industry employs a recovery, recycle, recharge or “R/R/R”machine to re-inject/re-fill refrigerant and lubricant into A/C systemsafter repair. However, the current R/R/R machine designed for use withHFO-1234yf, which is based on SAE J2843, particularly section 8.9.5.1 ofsaid SAE standard (hereby incorporated by reference), does not allowautomatic injection of lubricant into the system after repair by theR/R/R machine. The lubricant must be “hand injected” or “mechanicallyinjected.” For each of these options, the lubricant is filled into aninjector and then a hose is attached to the low side of the A/C system.The vehicle is turned on, and the A/C system set to maximum cooling,which also starts the A/C compressor. When the A/C compressor starts tocycle, the attached injector is turned to the open position andlubricant is conveyed along the hose to the A/C system.

While this method can be used, it is a tedious process and requires useof a hand-pump type mechanism that pushes the lubricant down theconnected hose to an A/C service port. Lubricant is pulled into thesystem by the A/C compressor. Lubricant can adhere to the walls of thehose during the delivery process thereby making it difficult to deliveryan appropriate amount of lubricant into the system. Therefore, there isa need in this art for a quick and convenient way to convey lubricantinto the A/C or heating system without the use of a hand injector.

There is also a need in this art for a quick and convenient way toconvey lubricant into the stationary A/C or heating system or therefrigeration without the use of a hand injector or vacuum pump.

For certain applications, it may be advantageous to use a similardelivery process to deliver refrigerant, refrigerant containinglubricant or refrigerant containing other performance enhancingadditives into the stationary A/C system using this same method ofconveyance

SUMMARY

Certain embodiments of the instant disclosure, solve problems associatedwith conventional compositions, systems and methods by providing a lowGWP refrigerant that can be used to inject lubricant into the low GWPHFO-1234yf automotive A/C system including through use of a typical A/Cto aftermarket recharging hose. In the hand injector or hand pump,lubricant flow is controlled by the lubricant viscosity and suction ofthe A/C compressor. In the inventive method, refrigerant is used toconvey the lubricant and/or lubricant additive package down the A/C hosewithout sticking on the hose thereby ensuring more lubricant orlubricant/additive package is introduced into the A/C system, therebymaterial flow is improved.

Using the hand injector or hand pump can lead to lubricant adhering tothe hose lines connecting to the A/C system. Use of the refrigerant totransfer the lubricant to the system ensures that more lubricant isintroduced into the A/C system versus the hand or pump injectors as therefrigerant carries the lubricant and conveys the lubricant into the A/Csystem. The lubricant or lubricant/additive and refrigerant areco-packaged into a conventional container (e.g., a can) under conditionsin which the lubricant and refrigerant are miscible. Upon leaving thesmall can, the refrigerant will change state from compressed liquefiedgas to refrigerant gas. During this process, refrigerant which ismiscible with the lubricant will atomize the lubricant orlubricant/additive mixture and will convey the lubricant orlubricant/additive mixture further along the hose and into the A/Csystem before the lubricant or lubricant/additive mixture can settle outon the A/C recharge hose walls.

One aspect of the invention relates to a composition comprising about 50to about 80 wt % POE lubricant and about 20 to about 50 wt % low GWPrefrigerant.

Another aspect of the invention relates to a composition comprisingabout 60 to about 65wt % POE lubricant and about 35 to about 40 wt % lowGWP refrigerant.

Another aspect of the invention relates to the foregoing compositionfurther comprising about 1 to about 5 wt % acid scavengers.

Another aspect of the invention relates to any of the foregoingcompositions further comprising about 1 to about 5 wt % performanceenhancers.

A further aspect of the relates to any of the foregoing compositionsfurther comprising about 1 to about 10 wt % of flame suppressants.

One aspect of the invention relates to a container comprising any of theforegoing compositions for use to directly deliver the composition intoa vehicle A/C system.

One aspect of the invention relates to a method for delivering a POElubricant into the vehicle A/C system using any of the foregoingcomposition or containers.

Another aspect of the invention comprises the foregoing method andfurther comprising delivering acid scavengers into the vehicle A/Csystem.

Another aspect of the invention comprises the foregoing methods andfurther comprising delivering performance enhancers into the vehicle A/Csystem.

Another aspect of the invention comprises the foregoing methods andfurther comprising delivering flame suppressants into the vehicle A/Csystem.

A further aspect of the invention comprises the foregoing methodswherein the method is conducted under pressure and temperatureconditions under which the lubricant is miscible with the refrigerant.

One aspect of the invention comprises a system for delivering any of theforegoing compositions, methods and container to an automotive A/C orHeating system comprising: a container comprising the composition, acompressor, condenser, dryer, expansion valve, and an evaporator.

Another aspect of the invention comprises a system for delivering any ofthe foregoing compositions, methods and container to a stationaryA/C/Heating system comprising: a container comprising the composition, acompressor, condenser, dryer, expansion valve, and an evaporator withcapillary tube.

And finally, another aspect of the invention comprises a system fordelivering any of the foregoing compositions, methods and container to astationary refrigeration system comprising: a container comprising thecomposition, a compressor, condenser, dryer, expansion valve, flash tankand an evaporator.

Another aspect of the invention relates to a composition comprisingabout 1 to about 15 wt % POE lubricant and about 85 to about 99 wt % lowGWP refrigerant.

Another aspect of the invention relates to a composition comprisingabout 1 to about 10 wt % POE lubricant and about 90 to about 99 wt % lowGWP refrigerant.

A further aspect of this invention relates to a composition comprisingabout 1 to about 5 wt % POE lubricant and about 95 to about 99 wt % lowGWP refrigerant

The various aspects and embodiments disclosed herein can be used aloneor in various combinations with each other.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic drawing of a system for introducing the inventivecomposition to a conventional A/C vehicular system.

FIG. 2 is a schematic drawing of a system for introducing the inventivecomposition to an electric type vehicle A/C or heating system.

FIG. 3 is a schematic drawing of system for introducing the inventivecomposition to a stationary type residential heating/cooling system.

FIG. 4 is a schematic drawing of system for introducing the inventivecomposition to a stationary type commercial refrigerating system.

DETAILED DESCRIPTION

The present invention relates generally to compositions comprising,consisting essentially of and in some cases consisting of lubricants,and additives, that are designed to work with environmentally friendlyrefrigerants. More specifically, this invention relates to compositionscomprising or consisting essentially of about 50 to about 80 wt %, about55 to about 70 wt %, or about 60 to about 65 wt % POE lubricants, about0 to about 5 wt % additives and about 20 to about 50 wt %, about 30 wt %to about 45 wt %, or about 35 wt % to about 40 wt low GWP refrigerantsor refrigerant blends and.

This invention can also relate to compositions comprising or consistingessentially of about 1 to about 15 wt %, about 1 to about 10 wt %, orabout 1 to about 5 wt % POE lubricants, about 0 to about 5 wt %additives and about 85 to about 99 wt %, about 90 wt % to about 99 wt %,or about 95 wt % to about 99 wt % low GWP refrigerants or refrigerantblends.

Lubricant

The lubricant used for this composition preferably has sufficientsolubility in the vehicle's A/C refrigerant to ensure that the lubricantcan return to the compressor from the evaporator. Furthermore, thelubricant preferably has a relatively low viscosity at low temperaturesso that the lubricant is able to pass through an evaporator (e.g., a lowtemperature evaporator). In one embodiment, the lubricant and A/Crefrigerant are miscible over a broad range of temperatures. Preferredlubricants may be one or more polyol ester type lubricants (POEs).Polyol ester as used herein include compounds containing an ester of adiol or a polyol having from about 3 to 20 hydroxyl groups and a fattyacid having from about 1 to 24 carbon atoms is preferably used as thepolyol.

An ester which can be used as the base oil, for example, as disclosed byEP 2 727 980 A1hereby incorporated by reference

Here, examples of the diol include ethylene glycol, 1,3-propanediol,propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol,2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol,2-methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol,1,12-dodecanediol, and the like.

Examples of the above-described polyol include a polyhydric alcohol suchas trimethylolethane, trimethylolpropane, trimethylolbutane,di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol,di(pentaerythritol), tri(pentaerythritol), glycerin, polyglycerin (dimerto eicosamer of glycerin), 1,3,5-pentanetriol, sorbitol, sorbitan, asorbitol-glycerin condensate, adonitol, arabitol, xylitol, mannitol,etc.; a saccharide such as xylose, arabinose, ribose, rhamnose, glucose,fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose,trehalose, sucrose, raffinose, gentianose, melezitose, etc.; partiallyetherified products and methyl glucosides thereof; and the like. Amongthese, a hindered alcohol such as neopentyl glycol, trimethylolethane,trimethylolpropane, trimethylolbutane, di(trimethylolpropane),tri(trimethylolpropane), pentaerythritol, di(pentaerythritol),tri(pentaerythritol), etc. is preferable as the polyol.

Though the fatty acid is not particularly limited on its carbon number,in general, a fatty acid having from 1 to 24 carbon atoms is used. Inthe fatty acid having from 1 to 24 carbon atoms, a fatty acid having 3or more carbon atoms is preferable, a fatty acid having 4 or more carbonatoms is more preferable, a fatty acid having 5 or more carbon atoms isstill more preferable; and a fatty acid having 10 or more carbon atomsis the most preferable from the standpoint of lubricating properties. Inaddition, a fatty acid having not more than 18 carbon atoms ispreferable; a fatty acid having not more than 12 carbon atoms is morepreferable, and a fatty acid having not more than 9 carbon atoms isstill more preferable from the standpoint of compatibility with therefrigerant.

In addition, the fatty acid may be either of a linear fatty acid and abranched fatty acid, and the fatty acid is preferably a linear fattyacid from the standpoint of lubricating properties, whereas it ispreferably a branched fatty acid from the standpoint of hydrolysisstability. Furthermore, the fatty acid may be either of a saturatedfatty acid and an unsaturated fatty acid.

Specifically, examples of the above-described fatty acid include alinear or branched fatty acid such as pentanoic acid, hexanoic acid,heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoicacid, dodecanoic acid, tridecanoic acid, tetradecanoic acid,pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoicacid, nonadecanoic acid, icosanoic acid, oleic acid, etc.; a so-calledneo acid in which a carbon atom thereof is quaternary; and the like.More specifically, preferred examples thereof include valeric acid(n-pentanoic acid), caproic acid (n-hexanoicacid), enanthic acid(n-heptanoic acid), caprylic acid (n-octanoic acid), pelargonic acid(n-nonanoic acid), capric acid (ndecanoic acid), oleic acid(cis-9-octadecenoic acid), isopentanoic acid (3-methylbutanoic acid),2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid,3,5,5-trimethylhexanoic acid, and the like. Incidentally, the polyolester maybe a partial ester in which the hydroxyl groups of the polyolremain without being fully esterified; a complete ester in which all ofthe hydroxyl groups are esterified; or a mixture of a partial ester anda complete ester, with a complete ester being preferable.

In the polyol ester, an ester of a hindered alcohol such as neopentylglycol, trimethylolethane, trimethylolpropane, trimethylolbutane,di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol,di(pentaerythritol), tri(pentaerythritol), etc. is more preferable, withan ester of neopentyl glycol, trimethylolethane, trimethylolpropane,trimethylolbutane, or pentaerythritol being still more preferable, fromthe standpoint of more excellent hydrolysis stability; and an ester ofpentaerythritol is the most preferable from the standpoint of especiallyexcellent compatibility with the refrigerant and hydrolysis stability.

Preferred specific examples of the polyol ester include a diester ofneopentyl glycol with one kind or two or more kinds of fatty acidsselected from valeric acid, caproic acid, enanthic acid, caprylic acid,pelargonic acid, capric acid, oleic acid, isopentanoic acid,2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and3,5,5-trimethylhexanoic acid; a triester of trimethylolethane with onekind or two or more kinds of fatty acids selected from valeric acid,caproic acid, enanthic acid, caprylic acid, pelargonic acid, capricacid, oleic acid, isopentanoic acid, 2-methylhexanoic acid,2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoicacid; a triester of trimethylolpropane with one kind or two or morekinds of fatty acids selected from valeric acid, caproic acid, enanthicacid, caprylic acid, pelargonic acid, capric acid, oleic acid,isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid,2-ethylhexanoic acid, and 3, 5, 5-trimethylhexanoic acid; a triester oftrimethylolbutane with one kind or two or more kinds of fatty acidsselected from valeric acid, caproic acid, enanthic acid, caprylic acid,pelargonic acid, capric acid, oleic acid, isopentanoic acid,2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and3,5,5-trimethylhexanoic acid; and a tetraester of pentaerythritol withone kind or two or more kinds of fatty acids selected from valeric acid,caproic acid, enanthic acid, caprylic acid, pelargonic acid, capricacid, oleic acid, isopentanoic acid, 2-methylhexanoic acid,2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoicacid.

Incidentally, the ester with two or more kinds of fatty acids may be amixture of two or more kinds of esters of one kind of a fatty acid and apolyol, and an ester of a mixed fatty acid of two or more kinds thereofand a polyol, particularly an ester of a mixed fatty acid and a polyolis excellent in low-temperature properties and compatibility with therefrigerant.

In a preferred embodiment, the lubricant is soluble in the vehicle A/Csystem refrigerant at temperatures between about 0° C. and about 100°C., and more preferably in the range of about 0° C. and about 40° C.,and even more specifically between 5° C. and 40° C. In anotherembodiment, attempting to maintain the lubricant in the compressor isnot a priority and thus high temperature solubility is not preferred. Inthis embodiment, the lubricant is soluble at temperatures above about70° C., more preferably at temperatures above about 80° C., and mostpreferably at temperatures between 90-95° C.

The lubricant used for electrified automotive air-conditioningapplication may have a kinematic viscosity (measured at 40° C.,according to ASTM D445) between 75-110 cSt, and ideally about 80 cSt-100cSt and most specifically, between 85 cst-95 cSt. However, not wantingto limit the invention, it should be noted that other lubricantviscosities may be included depending on the needs of the electrifiedvehicle A/C compressor.

Table 1 illustrates suitable characteristics of an automotive lubricantfor use with the inventive composition.

TABLE 1 Specification Item Units Method POE Properties Viscosity at 40°C. cSt ASTM D445 80-90 Viscosity at 100° C. cSt ASTM D445 9.0-9.3Viscosity Index ASTM D2270 >80 Colour Gardner ASTM D1500  <1 Flash point(COC) ° C. ASTM 92 250 min Pour point ° C. ASTM D97 −40 max SpecificGravity (20° C.) Kg/m3 ASTM D1298 0.950-1.10  Capping Efficiency % ASTME326 80-90 Total Acid Number mgKOH/g ASTM D974 0.1 max Water content ppmASTM E284  50 max

Additionally, the POE lubricant that are used in this composition shouldhave material compatibility with the elastomers and plastics used intypical vehicle A/C systems. The POE lubricant that is used should havegood material compatibility with, such as, Neoprene WRT(polychloroprene/2,3-dichloro-1,3-butadiene copolymer), HNBR(hydrogenated nitrile butadiene rubber), NBR (nitrile butadiene rubber),EPDM (ethylene propylene diene monomer), silicone and butyl rubber asmeasured by ASHRAE 97: 2007 “Sealed Glass Tube Method to Test theChemical Stability of Materials for Use within Refrigerant Systems” fortwo weeks at 100° C. Similarly, the POE lubricants used should have goodmaterial compatibility with plastic materials namely polyester, nylon,epoxy, polyethylene, terephthalate and polyimide as measured by ASHRAE97: 2007 “Sealed Glass Tube Method to Test the Chemical Stability ofMaterials for Use within Refrigerant Systems” for two weeks at 100° C.The plastics and elastomers in conjunction with the said POE lubricantsand HFO-1234yf should have a less than about 10%, less than about 8%, orless than about 7% wt gain or less than about 10%, less than about 8%,or less than about 7% linear swell or less than about 10, less thanabout 8, or less than about 7 hardness change as measured by adurometer. Ideally, the plastics and elastomers will have less than a10% wt gain or less than 10% linear swell or less than about 10 hardnesschange in at least two properties, as measured by a durometer,preferably, less than 10% for all three properties.

Several POE lubricants were found that had the required miscibility witha particular low GWP refrigerant, namely HFO-1234yf (available from TheChemours Company as Opteon™ refrigerants), over the desired temperaturerange, had the desired lubricant viscosity and had the desiredelastomer/plastics material compatibility. Specifically, the POEs arecommercially noted as automotive type POE lubricant and known by thefollowing tradenames “ND-11” and “SE-10Y”. Acceptable POE lubricants forstationary use were “Emkarate RL 32 3MAF”, “Emkarate RL32H” and “Solest35”.

Refrigerant

The refrigerant portion of the inventive composition comprises at leastone hydrofluoro-olefin or more commonly called an HFO type refrigerant,but it not limited to one particular HFO refrigerant.Hydrofluoro-olefins are low global warming potential (GWP) and zeroozone depletion potential (ODP). The Intergovernmental Panel on ClimateChange (IPCC) periodically reviews and establishes the GWP forfluorocarbons. The hydrofluoro-olefin refrigerant embodied in thisinvention has a GWP less than about 100 GWP, but typically has GWP lessthan 10 and even as low as 1 GWP. A particular useful hydrofluoro-olefincomprises HFO-1234yf. HFO-1234yf exhibits a GWP of less than 1 accordingthe UN'sIPCC Fifth Assessment Report (AR5).

Global warming potential (GWP) is an index for estimating relativeglobal warming contribution due to atmospheric emission of a kilogram ofa particular greenhouse gas compared to emission of a kilogram of carbondioxide. GWP can be calculated for different time horizons showing theeffect of atmospheric lifetime for a given gas. The GWP for the 100 yeartime horizon is commonly the value referenced. For mixtures, a weightedaverage can be calculated based on the individual GWPs for eachcomponent.

Leck et al. (US Patent Application Publication No. 2007/0187639,paragraph 10, hereby incorporated by reference) further lists examplesof unsaturated fluorocarbon refrigerants which may be used as thefluoro-olefins in the present invention. As set forth in paragraph 10 ofLeck et al., representative unsaturated fluorocarbon refrigerants orheat storage fluids include 1,2,3,3,3-pentafluoro-1-propene,1,1,3,3,3-pentafluoro-1-propene, 1,1,2,3,3-pentafluoro-1-propene,1,2,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene,1,3,3,3-tetrafluoro-1-propene,1,1,2,3-tetrafluoro-1-propene,1,1,3,3-tetrafluoro-1-propene,1,2,3,3-tetrafluoro-1-propene, 2,3,3-trifluoro-1-propene,3,3,3-trifluoro-1-propene, 1,1,2-trifluoro-1-propene,1,1,3-trifluoro-1-propene, 1,2,3-trifluoro-1-propene,1,3,3-trifluoro-1propene, 1,1,1,2,3,4,4,4-octafluoro-2-butene,1,1,2,3,3,4,4,4-octafluoro-1-butene, 1,1,1,2,4,4,4-heptafluoro-2-butene,1,2,3,3,4,4,4-heptafluoro-1-butene, 1,1,1,2,3,4,4-heptafluoro-2-butene,1,3,3,3-tetrafluoro-2-(trifluoromethyl)-2-propene,1,1,3,3,4,4,4-heptafluoro-1-butene, 1,1,2,3,4,4,4-heptafluoro-1-butene,1,1,2,3,3,4,4-heptafluoro-1-butene, 2,3,3,4,4,4-hexafluoro-1-butene,1,1,1,4,4,4-hexafluoro-2-butene, 1,3,3,4,4,4-hexafluoro-1-butene,1,2,3,4,4,4-hexafluoro-1-butene, 1,2,3,3,4,4-hexafluoro-1-butene 1,1,2,3,4,4-hexafluoro-2-butene, 1,1,1,2,3,4-hexafluoro-2-butene,1,1,1,2,3,3-hexafluoro-2-butene, 1,1,1,3,4,4-hexafluoro-2-butene,1,1,2,3,3,4-hexafluoro-1-butene, 1,1,2,3,4,4-hexafluoro-1-butene,3,3,3-trifluoro-2-(trifluoromethyl)-1-propene,1,1,1,2,4-pentafluoro-2-butene, 1,1,1,3,4-pentafluoro-2-butene,3,3,4,4,4-pentafluoro-1-butene, 1,1,1 ,4,4-pentafluoro-2-butene,1,1,1,2,3-pentafluoro-2-butene, 2,3,3,4,4-pentafluoro-1-butene,1,1,2,4,4-pentafluoro-2-butene, 1,1,2,3,3-pentafluoro-1-butene,1,1,2,3,4-pentafluoro-2-butene, 1,2,3,3,4 pentafluoro-1-butene,1,1,3,3,3-pentafluoro-2-methyl-1-propene,2-(difluoromethyl)-3,3,3-trifluoro-1-propene,3,3,4,4-tetrafluoro-1-butene, 1,1,3,3-tetrafluoro-2-methyl-1-propene,1,3,3,3-tetrafluoro-2-methyl-1-propene,2-(difluoromethyl)-3,3-difluoro-1-propene, 1,1,1,2-tetrafluoro-2-butene, 1,1,1 ,3-tetrafluoro-2-butene,1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene,1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene,1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene,1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene,1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene,1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene,1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene,1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene,1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene,1,1,1,12,3,4,4,5,5-nonafluoro-2-pentene,1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene,1,2,3,4,4,4-hexafluoro-3(trifluoromethyl)-1-butene,1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene,1,1,1,4,4,4-hexafluoro-3-(trifluoromethyl)-2-butene,1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene,2,3,3,4,4,5,5,5-octafluoro-1-pentene, 1,2,3,3,4,4,5,5-octafluoro-1-pentene,3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene,1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene,1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene,1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene,1,1,1,4,4,5,5,5-octafluoro-2-pentene,3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene,3,3,4,4,5,5,5-heptafluoro-1-pentene,2,3,3,4,4,5,5-heptafluoro-1-pentene,1,1,3,3,5,5,5-heptafluoro-1-pentene, 1,1,1,2,4,4,4-heptafluoro-3-methyl2-butene,2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene,1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene,1,4,4,4-tetrafluoro-3-(trifluoromethyl)-2-butene,2,4,4,4-tetrafluoro-3-(trifluoromethyl)-2-butene,3-(trifluoromethyl)-4,4,4-trifluoro-2-butene,3,4,4,5,5,5-hexafluoro-2-pentene, 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene, 3,3,4,5,5,5-hexafluoro-1-pentene,4,4,4-trifluoro-2-(trifluoromethyl)-1-butene,1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene,1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene,1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene,1,1,1,4,4,5,5,5-octafluoro-2trifluoromethyl-2-pentene,1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene,1,1,1,4,5,5,5-heptafluoro-4 (trifluoromethyl)-2-pentene,1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene,1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene,3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene,4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene,1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene,2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene,1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene,1,1,1,5,5,5-hexafluoro-4(trifluoromethyl)-2-pentene,3,4,4,5,5,6,6,6-octafluoro-2-hexene,3,3,4,4,5,5,6,6-octafluoro-2-hexene,1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene,4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene,3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene,1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene,1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene,1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene,1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene,1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene,1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene,4,4,5,5,6,6,6-heptafluoro-2-hexene, 4,4,5,5,6,6,6-heptafluoro-1-hexene,1,1,1,2,2,3,4-heptafluoro-3-hexene,4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene,1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene,1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene,1,2,3,3,4,4-hexafluorocyclobutene, 3,3,4,4-tetrafluorocyclobutene,3,3,4,4,5,5-hexafluorocyclopentene,1,2,3,3,4,4,5,5-octafluorocyclopentene,1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene, 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene, pentafluoroethyltrifluorovinyl ether, trifluoromethyl trifluorovinyl ether; or anycombination thereof.

Additionally, there could be one or more non-low GWP refrigerantcomponents comprising the refrigerant portion. Minor et al. (U S PatentApplication Publication No. 2007/0289317, hereby incorporated byreference) further lists examples of saturated and unsaturatedfluorocarbon refrigerants which may be used as the fluoroalkane in thepresent invention. As set forth in paragraph 81 of Minor et al.,representative hydrofluorocarbons may be represented by the formulaCxH2x+2_yFy or CxH2x_yFy, Where, x may equal 3 through 8 and y may equal1 through 17. The hydrofluorocarbons may be straight chain, branchedchain or cyclic; saturated or unsaturated compounds having from about 3to 8 carbon atoms. Without limitation, exemplary fluoroalkanes which maybe used, as set forth in Minor et al. paragraphs 47-78, include:1,1,2,2,3-pentafluoropropane, 1,1,1,3,3-pentafluoropropane;1,1,3-trifluoropropane, 1,1,3-trifluoropropane, 1,3-difluoropropane;2-(difluoromethyl)-1,1,1,2,3,3-hexafluoropropane,1,1,2,2,3,3,4,4-octafluorobutane; 1,1,1,2,2,4-hexafluorobutane;1,1,1,3,3-pentafluorobutane; 1,1-difluorobutane;1,3-difluoro-2-methylpropane, 1,2-difluoro-2-methylpropane;1,2-difluorobutane, 1,3-difluorobutane, 1,4-difluorobutane;2,3-difluorobutane;1,1,1,2,3,3,4,4-octafluoro-2-(trifluoromethyl)butane,1,1,1,2,2,3,3,4,4,5,5-undecafluoropentane,1,1,1,2,2,3,4,5,5,5-decafluoropentane;1,1,1,2,2,3,3,5,5,5-decafluoropentane,

The refrigerant or refrigerant blend portion of said invention will haveGWP less than 300, but specifically less than 150 GWP and morespecifically less than 75 GWP and ideally less than 5 GWP. It ispossible that a refrigerant is used such that the GWP<1.

The refrigerant portion of the blend mentioned above has a minimumignition energy (MIE) of at least 300 MJ/kg, preferably higher than1,000 MJ/kg, and more specifically between 1,000 MJ/kg to 5,000 MJ andeven more specifically at least 5,000 MJ/kg as measured by ASTM E-582.The heat of combustion, as calculated by the American Society ofHeating, Refrigeration and Air-conditioning Engineers (ASHRAE) Standard34, should be less than 19,000 kJ/kg and more specifically in the rangeof 8-12 kJ/kg and even more specifically, 9.5-11.5 kJ/kg. The lowerflammability limit at 21° C. of the refrigerant portion may actual benon-flammable as measured by ASTM E-681. Alternatively, if therefrigerant portion has flammability limits, the lower flammabilitylimit may be at least 5 volume % but more specifically at least 6 volume% and even more specifically, at least 6.2 volume % as measured by ASTME-681.

The overall resulting composition, i.e. lubricant and refrigerantmentioned herein can be “post-added” to the A/C system, advantageouslyhas relatively low corrosivity, such that a metal (e.g., aluminum,copper, or iron) which is part of the A/C system in contact with thecomposition experiences relatively low corrosion. Additionally, aftertesting for 14 days at 175° C., there was no dulling of the steel, nocoating or visible corrosion to the metals coupons and no deposits orflocs formed during testing.

The relatively low corrosivity of the lubricant/ refrigerant compositionmay be such that the refrigerant composition portion advantageouslyexhibits one or any combination of the following properties. A totalacid number (TAN), after aging per ASHRAE 97: 2007 “Sealed Glass TubeMethod to Test the Chemical Stability of Materials for Use withinRefrigerant Systems” for 14 days at 175° C., less than 3.3 mg KOH/g, andless than 1.5 mg KOH/g and specifically less than 1.0 mg KOH/g asmeasured per ASTM D664-01. With aluminum, copper and carbon steel metalstrips; a total halides concentration (e. g., a fluorine ionconcentration) of less than about 100 ppm, preferably less than 50 ppmand ideally less than 10 ppm after aging per ASHRAE 97: 2007 “SealedGlass Tube Method to Test the Chemical Stability of Materials for Usewithin Refrigerant Systems” for 14 days at 175° C. With aluminum, copperand iron metal strips, as measured by ion chromatography; a totalorganic acid concentration of less than about 300 ppm after aging perASHRAE 97: 2007 “Sealed Glass Tube Method to Test the Chemical Stabilityof Materials for Use within Refrigerant Systems” for 14 days at 175° C.

Additives which can improve the refrigerant and A/C lifetime andcompressor durability are desirable. In one aspect of the invention, theinventive refrigerant containing composition is used to introducelubricant into the A/C system as well as other additives, such as a)acid scavengers, b) performance enhancers, and c) flame suppressants.

Acid Scavenger

An acid scavenger may comprise a siloxane, an activated aromaticcompound, or a combination of both. Serrano et all (paragraph 38), whichis hereby incorporated by reference, discloses that the siloxane may beany molecule having a siloxyfunctionality. The siloxane may include analkyl siloxane, an aryl siloxane, or a siloxane containing mixtures ofaryl and alkyl substituents. For example, the siloxane may be an alkylsiloxane, including a dialkylsiloxane or a polydialkylsiloxane.Preferred siloxanes include an oxygen atom bonded to two silicon atoms,i.e., a group having the structure: SiiOiSi. For example, the siloxanemay be a siloxane of Formula IV: R1[Si(R2R3)4O]nSi(R2R3)R4. Where n is 1or more. Siloxanes of Formula IV have n that is preferably 2 or more,more preferably 3 or more, (e.g., about 4 or more). Siloxanes of formulaIV have n that is preferably about 30 or less, more preferably about 12or less, and most preferably about 7 or less. Preferably the R4 group isan aryl group or an alkyl group. Preferably the R2 groups are arylgroups or alkylgroups or mixtures thereof. Preferably the R3 groups arearyl groups or alkyl groups or mixtures thereof. Preferably the R4 groupis an aryl group or an alkyl group. Preferably R1, R2, R3, R4, or anycombination thereof are not hydrogen. The R2 groups in a molecule may bethe same or different. Preferably the R2 groups in a molecule are thesame. The R2 groups in a molecule may be the same or different from theR3 groups. Preferably, the R2 groups and R3 groups in a molecule are thesame. Preferred siloxanes include siloxanes of Formula IV, wherein R1,R2, R3, R4, R5, or any combination thereof is a methyl, ethyl, propyl,or butyl to group, or any combination thereof. Exemplary siloxanes thatmay be used include hexamethyldisiloxane, polydimethylsiloxane,polymethylphenylsiloxane, dodecamethylpentasiloxane,decamethylcyclo-pentasiloxane, decamethyltetrasiloxane,octamethyltrisiloxane, or any combination thereof.

Incorporated by reference from Serrano et al paragraph [0039] notes thatin one aspect of the invention, the siloxane is an alkylsiloxanecontaining from about 1 to about 12 carbon atoms, such ashexamethyldisiloxane. The siloxane may also be a polymer such aspolydialkylsiloxane, where the alkyl group is a methyl, ethyl, propyl,butyl, or any combination thereof. Suitable polydialkylsiloxanes have amolecular weight from about 100 to about 10,000. Highly preferredsiloxanes include hexamethyldisiloxane, polydimethylsiloxane, andcombinations thereof. The siloxane may consist essentially ofpolydimethylsiloxane, hexamethyldisoloxane, or a combination thereof.

The activated aromatic compound may be any aromatic molecule activatedtowards a Friedel-Crafts addition reaction, or mixtures thereof. Anaromatic molecule activated towards a Friedel-Crafts addition reactionis defined to be any aromatic molecule capable of an addition reactionwith mineral acids. Especially aromatic molecules capable of additionreactions with mineral acids either in the application environment (ACsystem) or during the ASHRAE 97: 2007 “Sealed Glass Tube Method to Testthe Chemical Stability of Materials for Use within Refrigerant Systems”thermal stability test. Such molecules or compounds are typicallyactivated by substitution of a hydrogen atoms of the aromatic ring withone of the following groups: NH2, NHR, NRz, ADH, AD, NHCOCH3, NHCOR,4OCH3, OR, CH3, 4C2H5, R, or C6H5, where R is a hydrocarbon (preferablya hydrocarbon containing from about 1 to about 100 carbon atoms). Theactivated aromatic molecule may be an alcohol, or an ether, where theoxygen atom (i.e., the oxygen atom of the alcohol or ether group) isbonded directly to an aromatic group. The activated aromatic moleculemay be an amine Where the nitrogen atom (i.e., the nitrogen atom of theamine group) is bonded directly to an aromatic group. By way of example,the activated aromatic molecule may have the formula ArXRn, Where X is O(i.e., oxygen) or N (i.e., nitrogen); n:1 When X:O; n:2 When x:N; Ar isan aromatic group (i.e., group, C6H5); R may be H or a carbon containinggroup; and When n:2, the R groups may be the same or different. Forexample, R may be H (i.e., hydrogen), Ar, an alkyl group, or anycombination thereof, exemplary activated aromatic molecules that may beemployed in a refrigerant composition according to the teachings hereininclude diphenyl oxide (i.e., diphenyl ether), methyl phenyl ether(e.g., anisole), ethyl phenyl ether, butyl phenyl ether or anycombination thereof. One highly preferred aromatic molecule activated toWards a Friedel-Crafts addition reaction is diphenyl oxide.

Incorporated by reference from Serrano et al paragraph [0045] The acidscavenger (e.g., the activated aromatic compound, the siloxane, or both)may be present in any concentration that results in a relatively lowtotal acid number, a relatively low total halides concentration, arelatively low total organic acid concentration, or any combinationthereof.

Preferably the acid scavenger is present at a concentration greater thanabout 0.0050 wt %, more preferably greater than about 0.05 wt % and evenmore preferably greater than about 0.1 wt % (e.g. greater than about 0.5wt %) based on the total Weight of the refrigerant composition. The acidscavenger preferably is present in a concentration less than about 3 wt%, more preferably less than about 2.5 wt %and most preferably greaterthan about 2 wt % (e. g. less than about 1.8 wt %) based on the totalWeight of the refrigerant composition.

Additional examples of acid scavengers Which may be included in therefrigerant composition and preferably are excluded from the refrigerantcomposition include those described by Kaneko (U.S. patent applicationSer. No. 11/575,256, published as U.S. Patent Publication 2007/0290164,paragraph 42, expressly incorporated herein by reference), such as oneor more of: phenyl glycidyl ethers, alkyl glycidyl ethers, alkyleneglycol glycidyl ethers, cyclohexene oxides, otolen oxides, or epoxycompounds such as epoxidized soybean lubricant, and those described bySingh et al. (U.S. patent application Ser. No. 11/250,219, published asU.S. Patent to Publication 2006/0116310, paragraphs 34-42, expresslyincorporated herein by reference).

Performance Enhancers

Preferred additives include those described in US. Pat. Nos. 5,152,926;4,755,316, which are hereby incorporated by reference. In particular,the preferred extreme pressure additives include mixtures of (A)tolyltriazole or substituted derivatives thereof, (B) an amine (e.g.Jeffamine M-600) and (C) a third component which is (i) an ethoxylatedphosphate ester (e.g. Antara LP-700 type), or (ii) a phosphate alcohol(e.g. ZELEC 3337 type), or (iii) a Zinc dialkyldithiophosphate (e.g.Lubrizol 5139, 5604, 5178, or 5186 type), or (iv) amercaptobenzothiazole, or (v) a 2,5-dimercapto-1,3,4-triadiaZolederivative (e. g. Curvan 826) or a mixture thereof. Additional examplesof additives which may be used are given in U.S. Pat. No. 5,976,399(Schnur, 5:12-6:51, hereby incorporated by reference).

Acid number is measured according to ASTM D664-01 in units of mg KOH/g.The total halides concentration, the fluorine ion concentration, and thetotal organic acid concentration is measured by ion chromatography.Chemical stability of the refrigerant system is measured according toASHRAE 97: 2007 “Sealed Glass Tube Method to Test the Chemical Stabilityof Materials for Use within Refrigerant Systems”. The viscosity of thelubricant is tested at 40° C. according to ASTM D-445.

Mouli et al. (WO 2008/027595) teaches the use of alkyl silanes as astabilizer in refrigerant compositions containing fluoroolefins.Phosphates, phosphites, epoxides, and phenolic additives also have beenemployed in certain refrigerant compositions. These are described forexample by Kaneko (U.S. patent application Ser. No. 11/575,256,published as U.S.

Publication 2007/0290164) and Singh et al. (U.S. patent application Ser.No. 11/250,219, published as U.S. Patent Publication 2006/0116310). Allof these aforementioned applications are expressly incorporated hereinby reference.

Flame Suppressants

Preferred flame suppressants include those described in patentapplication “Compositions containing fluorine substituted olefins CA2557873 A1” and incorporated by reference along with fluorinatedproducts such as HFC-125 and/or Krytox® lubricants, also incorporated byreference and described in patent application “Compositions comprisingfluoroolefins and uses thereof” WO 2009018117 A1.”

Miscibility/Package Stability

While HFO-1234yf when used as the main refrigerant for vehicle A/Csystems, is generally found to be compatible with polyol ester or POEtype lubricants, in certain environments, not all POE lubricants havethe required miscibility range, thermal stability, materialcompatibility, moisture level, among other characteristics to besuitable for use with HFO-1234yf in automotive A/C systems. Accordingly,the inventive composition is substantially free of POE lubricantslacking the foregoing characteristics. By “substantially free” it ismeant that when the inventive composition comprises HFO-1234yf thecomposition contains less than 5 wt %, typically less than 3 wt % and insome cases less than 0.5 wt % of the following POE Dow RL244, Zerol 150and 3GS. The amount of lubricant that is typically used in the A/C orRefrigeration system ranges from about 5 to about 10 wt % of the amountof the refrigerant. For example, a refrigerant charge of 600g, 60g oflubricant will be used (90 wt % refrig/10 wt % lubricant). However,since refrigerant will be used to transfer the lubricant into thesystem, the amount of POE lubricant that will be used in conjunctionwith refrigerant, will be relatively large, on the order of 50-80 wt %lubricant/20-50wt % refrigerant (e.g., about 60 to about 65 wt. %lubricant).

The major component of the inventive composition can comprise lubricant,while the minor component/s will comprise refrigerant, with some lowamount (0-5 wt %) of additives that improve a desired performanceproperty. That is, the refrigerant will be used to convey or transferthe liquid lubricant and additives into the A/C system.

The lubricant and refrigerant must have mutual miscibility over a muchgreater range due to storage and use conditions. There are many globalcities that experience temperatures exceeding 37.5° C. Additionally, itis expected that the lubricant/refrigerant composition would be storedat relatively hot warehouse or used in hot garage where temperaturescould reach as high as 37.5° C. for a period of greater than 70 days.

It is also conceivable that the product could be used during the wintermonths after a major vehicle system failure such as a front-endcollision. Therefore, the lubricant/refrigerant would be stored in coldwarehouse and brought into a garage only during servicing. Thelubricant/refrigerant composition is stable at temperatures of about−20, −30, −40 and even −50° C. which should aid in storing of saidcomposition at temperatures of −20° C. for longer periods such as 5days.

It was surprising that the inventive composition maintains miscibilityover a wide range of temperature and pressure conditions (e.g., acomposition 20-50 wt % refrigerant/50-80 wt % lubricant that is miscibleover a temperature range of -18° C. to 37° C. at a pressure of 160 kPato 945 kPa within a sealed container). POE lubricant/refrigerantmiscibility is conducted by loading predetermined amounts of lubricantsand refrigerants (see tables below) into sealed tubes using ASHRAE 97:2007 “Sealed Glass Tube Method to Test the Chemical Stability ofMaterials for Use within Refrigerant Systems” method. Then, the sealedtubes are set into water baths to determine if a mixture is miscibleover a range of temperatures. The test is conducted in two segments witha 24-hour period between each segment to allow tubes to come back toroom temperature prior to starting the next segment. The cold segment isstarted at room temperature and slowly decreases temperature to −50° C.in 5° C. increments holding at each temperature for 10 minutes andrecording visual observation at each temperature hold. The hot segmentis started at room temperature and slowly increases temperature to 90°C. or critical temperature of the refrigerant being tested in 5° C.increments and again holding at each temperature for 10 minutes andrecording visual observation at each temperature hold.

POE lubricant/refrigerant compositions were evaluated for thermalstability using ASHRAE 97: 2007 “Sealed Glass Tube Method to Test theChemical Stability of Materials for Use within Refrigerant Systems”. Thelubricant/refrigerant systems were also placed in sealed tubescontaining metal (Al, Cu, carbon steel) coupons and held at 175° C. fortwo weeks. Results indicate that the POE lubricant/low GWP refrigerant/sare thermally stable under elevated temperature which indicates thatcompositions should not break down during storage. There was no dullingof on the steel, no coating or visible corrosion to the metals and nofluoride ion or acid generation. No deposits or flocs formed duringtesting. There was no color change to the refrigerant/lubricant system.

An unexpected esult was that lubricants which were conventionally listedas “compatible with HFO-1234yf” do not have miscibility across theentire miscibility range. Specifically, the POEs are noted as 86cSt typePOE lubricant and known by the following tradenames “ND-11” and“SE-10Y”. Acceptable POE lubricants for stationary use were “EmkarateRL32- 3MAF”, “Emkarate RL32H” and “Solest 35”.

Without wishing to be bound by any theory or explanation, it is believedthat once the refrigerant concentration increases to become the majorportion of the composition, the lubricant/lubricant miscibility rangechanges. For example, a 30 wt % lubricant/70 wt % refrigerant would bemarginal for use in an A/C system, but lacks sufficient miscibility touse the refrigerant to transfer the lubricant into the system.

The conventional POE lubricants (Zerol 150 and 3GS) used with R-134a didnot have the same miscibility range with R-1234yf (unsaturated low GWPrefrigerant). Therefore, not all POE lubricants are useful for low GWPsystems.

Examples of the low GWP refrigerant/POE lubricant compositions andmiscibility range are shown in Table 2 where the upperportion of thetable shows product use in A/C system and the lowerportion of the tableshows manufacturing and storage temperatures (wherein “M” means miscibleand “N” means non-miscible).

TABLE 2 Lubricant: ND11 amt. refrigerant/ oil Temperature (C.) oil (ml)−50 −45 −40 −35 −30 −25 −20 −15 −10 −5 0 5 10 15 20 95/5%  0.1 M M M M MM M M M M M M M M M 90/10% 0.2 M M M M M M M M M M M M M M M 85/15% 0.3M M M M M M M M M M M M M M M 80/20% 0.4 M M M M M M M M M M M M M M M70/30% 0.6 M M M M M M M M M M M M M M M 40/60% 1.2 M M M M M M M M M MM M M M M 30/70% 1.4 M M M M M M M M M M M M M M M amt. refrigerant/ oilTemperature (C.) oil (ml) 25 30 35 40 45 50 55 60 65 70 75 80 85 9095/5%  0.1 M M M M M M M M M M M M N N 90/10% 0.2 M M M M M M M M M M MN N N 85/15% 0.3 M M M M M M M M M M N N N N 80/20% 0.4 M M M M M M M MM M N N N N 70/30% 0.6 M M M M M M M M M M N N N N 40/60% 1.2 M M M M MM M M M M M M M M 30/70% 1.4 M M M M M M M M M M M M M M

One aspect of the invention relates to a method for introducinglubricant into the A/C system. In the inventive method, refrigerant isused to convey the lubricant and/or lubricant additive package down theA/C hose substantially without adhering to the hose thereby ensuringmore lubricant or lubricant/additive package is introduced into the A/Csystem (e.g., using the hand injector or hand pump can lead to lubricantadhering to the hose lines connecting to the A/C system). Use of therefrigerant to transfer the lubricant to the system ensures that morelubricant is introduced into the A/C system versus the hand or pumpinjectors as the refrigerant carries the lubricant and conveys thelubricant into the A/C system. The lubricant or lubricant/additive andrefrigerant are co-packaged into a conventional container or can underconditions in which the lubricant and refrigerant are miscible. Uponleaving the small container, the refrigerant will change state fromcompressed liquefied gas to refrigerant gas. During this process,refrigerant which is miscible with the lubricant will atomize thelubricant or lubricant/additive mixture and will convey the lubricant orlubricant/additive mixture further along the hose and into the A/Csystem before the lubricant or lubricant/additive mixture can settle outon the A/C recharge hose walls.

In one aspect of the invention, the inventive composition (lubricant orlubricant/additive with refrigerant) can be packaged into a small sealedcontainer that is typically 8 oz or less, and more typically 3-6 oz andeven more specifically, 3-4oz.

In one embodiment, the inventive composition may be packaged in a smallcontainer that has a piercing can top or self-sealing can top that canbe connected to the vehicle's A/C system using a typical aftermarketrefrigerant recharging hose.

In one embodiment, the fittings used on the top of the can should beleft-hand thread and meet a male CGA 166 type connection as this productis intended to be used in a low GWP A/C system that contains

HFO-1234yf. The type of hose used to convey this product from the can tothe vehicle's A/C system should meet the SAE J2888 standard forconstruction. The hose should have two different fittings. One end ofthe A/C recharge hose should be able to connect to the small can andhave either a piercing needle or a plunger type mechanism, sometimescalled a can tap, which can liberate the product within the container.The fitting that connects to the can will be a female CGA 166 typefitting. The other end of the recharge hose should have the designatedSAE J639 low side quick connect coupler for HFO-1234yf and should beable to attach to the vehicle's A/C system through the low side serviceport.

In another aspect of the invention, the inventive composition (lubricantor lubricant/additive with refrigerant) can be packaged into a smallsealed container that is typically 8-12 oz or less. The inventivecomposition should be packaged in a small can that has a piercing cantop or self-sealing can top that can be connected to the stationarysystem using a typical aftermarket refrigerant recharging hose. Thefittings used on the top of the can should be left-hand thread and meeta male CGA 164 type connection if this product is intended to be used ina low GWP A/C system that is used for flammable refrigerant systems. Thefittings used on the top of the can should be left-hand thread and meeta male CGA 165 type connection if this product is intended to be used ina low GWP A/C system that is used for non-flammable refrigerant systems.

To convey the inventive composition into the A/C system, first the cancontaining the lubricant or lubricant/additive and refrigerant should bewell shaken. The vehicle's engine should be started and then the A/Csystem set to maximum cooling. Then, the aftermarket recharge hose asmentioned above, should be attached to the can. The other side of thehose should be connected to the vehicle's A/C low side service port.When ready to start dispensing the product, the needle or plungermechanism should be used to liberate the can contents. The can should beshaken slightly from side to side to help liberate the can contents.This process should take about 10-15 minutes.

The instant composition can be used for adding lubricant orlubricant/additive to the A/C system at temperatures between about 0° C.and about 40° C., more specifically, this composition can be used attemperatures of about 10° C. and about 35° C., and even morespecifically at temperatures of about 15° C. to about 30° C. Theinventive composition can be stored at temperatures as low as about −20°C. and as high as about 40 to about 45° C., but typically, it will bestored at temperatures of about 10 to about 35° C. and more specificallyat temperatures of about 15 to about 30° C. Typically, when connected tothe A/C system, the inventive composition will be delivered to the A/Csystem at pressures between about 315 kPa and about 435 kPa, or morespecifically between about 330 kPa and about 410 kPa, or even morespecifically at pressures between about 360 kPa and about 400 kPa.

Another aspect of the invention relates to a system for introducing theinventive composition into a heat management system such as anautomotive A/C system. Referring now to FIG. 1, FIG. 1 illustrates asystem (100) for introducing lubricant using the inventive compositioninto an automotive A/C system. The system for delivering the inventivecomposition to an automotive A/C system comprises a container (110)comprising the composition, a compressor (120), a condenser (130), adryer (140), an expansion valve (150), and an evaporator (160). Thesystem (100) additionally includes a low side service port (170) and ahigh side service port (180). A container (110) or can housing theinventive composition is connected via a hose (190) to a low sideservice port (170) of the compressor (120). The hose (190) and lines(195) connecting the compressor, condenser, dryer, expansion valve andevaporator are constructed and assembled using materials and methodsknown in the art.

Referring now to FIG. 2, FIG. 2 illustrates another aspect of theinvention that comprises a system (200) for introducing the inventivecomposition into an electric vehicle A/C system. This system forintroducing lubricant composition comprises a container (210) comprisingthe composition, an electric compressor (220), a condenser (230), adryer (240), an expansion valve (250) or orifice tube (251) and anevaporator (260). The system (200) additionally includes a low sideservice port (270) and a high side service port (280). The container(210) of the inventive composition is connected to the low side serviceport (270) of the electric compressor (220) via a hose (290). The hose(290) and lines (295) shown in FIG. 2 are constructed and assembledusing materials and methods known in the art.

Referring now to FIG. 3, FIG. 3 illustrates a further aspect of theinvention that comprises a system (300) for introducing the inventivecomposition into a residential stationary type heating/cooling system.This system (300) for introducing lubricant composition comprises acontainer (310) comprising the composition, a compressor/condenser (320)located on the exterior of a residence (330) and an evaporator/capillarytube (340) located on an interior of the residence (350). The container(310) is connected to a low side service port (360) of thecompressor/condenser (320) via a hose (370). The compressor/condenser(320) additionally includes a high side service port (380). The hose(370) and lines (390) shown in FIG. 3 are constructed and assembledusing materials and methods known in the art.

Referring now to FIG. 4, FIG. 4 illustrates another aspect of theinvention that comprises a commercial stationary type refrigeratingsystem (400). This system (400) for introducing lubricant compositioncomprises a container (410) comprising the composition, compressors(420), rooftop condensers (430), a flash tank (440) and definedrefrigerated area (450) within a commercial structure (460) (e.g., arefrigerated display cabinet). The container (410) is connected to a lowside service port (470) of the compressors (420) which can be locationremote from the defined refrigerated area (450) via a hose (480). Thehose (480) and lines (490) shown in FIG. 4 are constructed and assembledusing materials and methods known in the art.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a composition,process, method, article, or apparatus that comprises a list of elementsis not necessarily limited to only those elements but may include otherelements not expressly listed or inherent to such composition, process,method, article, or apparatus. Further, unless expressly stated to thecontrary, “or” refers to an inclusive or and not to an exclusive or. Forexample, a condition A or B is satisfied by any one of the following: Ais true (or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistsof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition, method that includes materials, steps, features,components, or elements, in addition to those literally disclosedprovided that these additional included materials, steps, features,components, or elements do materially affect the basic and novelcharacteristic(s) of the claimed invention, especially the mode ofaction to achieve the desired result of any of the processes of thepresent invention. The term ‘consisting essentially of’ occupies amiddle ground between “comprising” and ‘consisting of’.

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso include such an invention using the terms “consisting essentiallyof” or “consisting of.”

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Although certain aspects, embodiments and principals have been describedabove, it is understood that this description is made only way ofexample and not as limitation of the scope of the invention or appendedclaims.

What is claimed is:
 1. A composition comprising about 50 to about 80 wt% polyol ester lubricant and about 20 to about 50 wt % consistingessentially of 1234yf refrigerant, wherein the refrigerant exhibits aglobal warming potential (GWP) of less than about 150 wherein thelubricant is miscible with the refrigerant at over a temperature rangeof −18° C. to 37° C. at a pressure of 160 kPa to 945kPa within a sealedcontainer when measured using ASHRAE 97: 2007 and wherein the lubricantcomprises less than 50 ppm water when measured in accordance with ASTME284.
 2. The composition of claim 1 further comprising about 1 to about5 wt % acid scavengers.
 3. The composition of claim 2, wherein the acidscavengers comprise at least one member selected from the groupconsisting of hexamethyldisiloxane, polydimethylsiloxane,polymethylphenylsiloxane, dodecamethylpentasiloxane,decamethylcyclo-pentasiloxane, decamethyltetrasiloxane, oroctamethyltrisiloxane.
 4. The composition of claim 1 further comprisingabout 1 to about 5 wt % performance enhancers.
 5. The composition ofclaim 1 further comprising about 1 to about 10wt % of flamesuppressants.
 6. A container comprising the composition of claim 1configured to deliver the composition into a vehicle air conditioningsystem.
 7. The container of claim 6, wherein the pressure within thecontainer is 160 kPa to 945 kPa.
 8. The composition of claim 1 furthercomprising at least one member selected from the group consisting oftolyltriazole or substituted derivatives thereof, amines, ethoxylatedphosphate esters, phosphate alcohols, zinc dialkyldithiophosphates,mercaptobenzothiazoles and 2,5-dimercapto-1,3,4-triadiaZole derivatives.9. A method for delivering a POE lubricant into a vehicle airconditioning system comprising connecting a container comprising thecomposition of claim 1 to the vehicle air conditioning system andtransferring the composition of claim 1 into the vehicle airconditioning system.
 10. The method of claim 9 further comprisingdelivering acid scavengers, performance enhancers, or flame suppressantsinto the vehicle air conditioning system.
 11. The method of claim 9wherein at least a portion of the lubricant is atomized when deliveringthe lubricant into the vehicle air conditioning system and the vehiclecomprises an electrified vehicle.
 12. The method of claim 11, whereinthe pressure is between about 315kPa and about 435kPa and thetemperature is between about −18° C. and about 37° C.
 13. The method ofclaim 9, wherein the lubricant for the electric vehicle has and ASTMD445 viscosity selected from one of (1) between 75-110 cSt, (2) 80cSt-100 cSt. and (3) between 85 cst-95 cSt.
 14. A system for deliveringthe composition of claim 1 to an automotive air conditioning systemcomprising: a container comprising the composition of claim 1, anelectric compressor, a condenser, a dryer, an expansion valve, and anevaporator.
 15. A composition comprising about 50 to about 80 wt % of alubricant which consists essentially of polyol ester lubricants andabout 20 to about 50 wt % 1234yf refrigerant, wherein the refrigerantexhibits a global warming potential (GWP) of less than about 150 whereinthe lubricant is miscible with the refrigerant at over a temperaturerange of −18° C. to 37° C. at a pressure of 160 kPa to 945kPa within asealed container when measured using ASHRAE 97: 2007 and wherein thelubricant comprises less than 50 ppm water when measured in accordancewith ASTM E284.